Copper-containing disazo dyestuffs



Patented July 3, 195%;

United States Patent() 1C6 2,753,335

taining 3 to 12 carbon atoms, a carbalkoxy group, a substituted benzoyl group or a -CO.NH-mononuclear aryl group, 2753335 to a treatment with a copper yielding agent, e. g. to a COPPER-CONTAINING DISAZO DYESTUFFS 5 gentle boiling in an aqueous solution in the presence of Walter Wehrli Basel Switzerland assignor to Sandoz cuprammonium ions, an alkaline substance such as sodium 3 Q t Q carbonate or potassium carbonate and, if desired, of an Llmlted Basel Swltzefland organic base, or to a fusion with an alkali metal salt of No Drawing. Application September 30, 1952, a low molecular aliphatic monocarboxylic acid and a Serial No. 312,391 copper salt.

1 Claim. (CL .The coppering proceeds with splitting oh the methoxy roups attached to the diphenyl nucleus of the dyestufis, and uniform copper complexes which then can be isolated by salting out from the solution, are obtained. The present application is a continuation-impart ap- The new copper-containing disazo dyestuffs thus 0bplication of my copending application Ser. No, 206,312, tained correspond to the formula H018 (It--83. O 0-( )u( 0 110; 50,11 HOzS- N filed on January 16, 1951 (now U. S. Patent No. wherein R1 and R2 have the foregoing ,significancy. They 2,620,331), which itself is a divisional application of the are easily soluble in Water, possess excellent aifini-ty for application Ser. No. 604,727, filed on July 12, 1945, now cellulose fibers and dye them in bright blue shades of exabandoned. cellentfastness to light and Wet treatments.

The present invention relates to new copper complex The following examples illustrate the present invention compounds of disazo dyestuifs. without being limitative. The parts are parts .by weight It is a primary object of the present invention to suband the temperatures are given in centigrades,

' Example 1 100 parts of the dyestufi? of the formula Hols 0H H300 OCHz HOaS- 503B HOBS- NH- Cl jectin preparing the new copper complex compounds are dissolved in 2000 parts of water with addition of 20 according to the present invention-a starting compound parts of sodium carbonate. To this solution there are which corresponds to the formula added, portionwise and while stirring at 80-90 C., 500

110118 0H HsOO 00H: HO

110 8- 80:11 Hols N wherein R1 stands for the hydrogen atom or a lower alkyl. 4 i s p i group, and parts of an aqueous solution containing parts of crystal- Rz stands for a lower alkyl or cycloalkyl group, ,tt mo;noglized copper sulfate and 85 parts of a concentrated nuclear aryl group with the exception of phenyl, alkyl- 9 aqueous ammonia solution. The mixture is stirred for phenyl and alkoxypheuyl, a C0.alky l-;group con- 5 hours at -90 C. and heated to boiling within 1 hour.

2,753,335 e H 3 4 The solution is then held at the boil under reflux for 15 hours. The copper complex compound thus produced corresponds to the formula HOaS OCu Gu-O O 0 I I 1 l HOzS- S0311 HO3S- NEG Cl It is salted out, filtered and dried. Soluble in water with and otherwise proceeding in the same manner as dea blue coloration and in concentrated sulfuric acid with a scribed in such example, a similar dyestufi which corregreenish-blue coloration, it dyes cotton and fibers made sponds to the formula Boas o-ou--o oou-o nolssoln Ems NEG 0Q from regenerated cellulose in clear blue shades possessing 26 is obtained.

very good fastness to light, to washing and to water. Example 4 ExampleZ 50 parts of crystallized copper sulfate are dissolved in 100 Parts of the dyestuff of the formula 200 parts of water of 80 C. Then 350 parts of crystal- HO S OH HaCO OCH;

HO;S SOaH v Hms- NHQCI are dissolved in 2000 parts of water and treated as described in Example 1. A dyestuif which corresponds to 0 the formula no.5: oou -o O-Cu0 =N N=N nms sour riots NHQCI is obtained. It possesses similar fastness properties as the dyestufi of Example 1, when dyed on cotton and fibers lized sodium acetate are added, followed by 107 parts made from regenerated cellulose. of the dyestuff of the formula HO S OH H|CO OCH: HO

son; HOSS- NH.OO.HN

xample 3 65 The slurry is stirred for 4 hours at 90 C. and then boiled By replacing the starting dyestutf of Example 1 by an under reflux for 12.hours. After that time the slurry is equivalent quantlty of the dyestutf of the formula allowed to cool to 80 C., and water is added dropwise HOIS OH H200 OCH:

52353335 A 5 6 until all mineral salts are dissolved, the dyestutf not yet and possesses very .good fastuessrprbperties when dyed being in solution. The copper complex compound thus on cotton or fibers made from regenerated cellulose. it obtained corresponds to the formula v Ems 0--ou o O---( 3uO 1 a -1r=N N=1 I HO3S- soin H0! NZELOOHN-O it is filtered, washed and dried. Soluble in water with Exampled a blue coloration and in concentrated sulfuric acid with a greenish-blue coloration, it dyes cotton and fibers made 15 By replacing starting dyesmfi Example 1 by equivalent quantity of the dyestulf of the formula H038 OH H300 OOH; HO

noissotn Ho8s from regenerated cellulose in clear blue shades which and otherwise proceeding in the same manner as described possess a very good fastness to light, to washing and to in such example, a similar dyestulf which corresponds to water. the formula no,s oou--o o---ou-o nots- 80in Hots NHQOH 00H Example 5 The process according to Example 4 is repeated except is obtained the dyeings of which on cellulose fibers possess that the starting dyestufi is replaced by 113 parts of the when after-treatedwith a copper yielding agent, excellent dyestulf of the formula fastness properties.

H038 on 11 00 0e11, no

HO|S- S OzH H0;S NH. C 0 091519 The dyestuffs which correspond to the formula 1103 s 0- :u 0 nt-4 R1 HO; SOaH HO; N\

The resultant copper complex compound corresponds to and wherein R1 denotes hydrogen and R2 possesses the the formula significancy given hereinafter, dye shadegsimilar to those H038 (I)C u---O O-?u-O H033 503E HO: NILCO-CQHID 1 i s of the dyestufis described in Examples 1 to 6. Their fastness properties are very good. I Example RI Example RI O CIH! O CIHI O CIHI /CH2CH2 1a O-Br 36 -n /OH! I OH 30 I-OHI 14 B Example 37 parts of cotton are inserted in a dyebath containing Q 100 parts of lime-free water at 50. Then a concentrated H aqueous solution, containing 0.1 part of a dyestuff obtained according to one of the foregoing examples is added to the bath which is thereupon heated to boiling in the course of a half hour, the boiling temperature being OK then maintained for a further half hour. In the course 40 of the dyeing process, 0.5 to 2 parts of Glauber salts are (30011 added in the form of a concentrated aqueous solution.

Upon completion of the dyeing, the material is allowed to remain in the bath until it cools to whereupon it is rinsed and dried.

Having thus disclosed the invention what is claimed is: The copper-containing disazo dyestuif which corresponds to the formula I I I l I I z I I I I I I Q I III References Cited in the file of this patent UNITED STATES PATENTS 1,889,732 Stusser Nov. 29, 1932 2,590,346 Riat et al Mar. 25, 1952 2,620,331 Wehrli Dec. 2, 1952 2,638,468 Wehrli -2--. May 12, 1953 

